Computational and Theoretical Chemistry最新文献

{"title":"Study of optoelectronic, thermoelectric and induced half-metallicity in Wurtzite ZnS via codoped (Eu, Cr): A DFT method","authors":"W. Amghar ,&nbsp;A. Fakhim Lamrani ,&nbsp;E. Maskar ,&nbsp;A. El Hat ,&nbsp;R. Ahl Laamara ,&nbsp;A. Yvaz ,&nbsp;D.P. Rai","doi":"10.1016/j.comptc.2025.115533","DOIUrl":"10.1016/j.comptc.2025.115533","url":null,"abstract":"<div><div>Based on the Density Functional Theory (DFT), we have successfully examined the wurtzite sulfide (ZnS) codoped with the couple (Eu, Cr). This study calculates the electronic, magnetic, optical, and thermoelectric (TE) properties using the GGA and GGA + U methods. Our results find that the ferromagnetic alignment of spin is more stable than its antiferromagnetic coupling. Most notably, a half-metallic behaviour is observed in the codoped material, exhibiting 100 % spin polarization at the Fermi level. However, the origins of ferromagnetism in the complex Zn_1-2xEu_xCr_xS, x = 0.0625, are due to hybridization between S-3p, Cr-3d, and Eu-4f states in the case of the GGA approximation and p-f hybridization in the case of GGA + U. The insertion of double impurities leads to a compound with a large half-metallic gap. The optical simulation of ferromagnetic alloy reveals a high absorption coefficient at the ultraviolet spectrum level and a low reflectivity in the visible range. Furthermore, the calculation of the figure of merit ZT ∼ 1 proves that we have an efficient material for converting thermal energy into electricity. All these qualities combine to make <span><math><msub><mi>Zn</mi><mrow><mn>1</mn><mo>−</mo><mn>2</mn><mi>x</mi></mrow></msub><msub><mi>Eu</mi><mi>x</mi></msub><msub><mi>Cr</mi><mi>x</mi></msub><mi>S</mi></math></span> a half-metallic ferromagnetic material efficient for spintronic, optoelectronic, and thermoelectric applications.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1254 ","pages":"Article 115533"},"PeriodicalIF":3.0,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145263277","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrostatically embedded grid-adapted many-body analysis (EE-GAMA): A charge embedded fragment-based quantum chemistry method for accurate modelling of neutral and charged molecular clusters","authors":"Sujan Kundu ,&nbsp;Arjun Saha","doi":"10.1016/j.comptc.2025.115534","DOIUrl":"10.1016/j.comptc.2025.115534","url":null,"abstract":"<div><div>Accurate quantum mechanical modelling of large molecular systems remains a formidable challenge due to the steep computational scaling of conventional methods. Fragment-based quantum chemistry approaches offer a more efficient alternative, but their accuracy is often limited by the neglect of long-range inter-fragment electrostatic interactions. To overcome this, we introduce <strong>E</strong>lectrostatically <strong>E</strong>mbedded <strong>G</strong>rid-<strong>A</strong>dapted <strong>M</strong>any-<strong>B</strong>ody <strong>A</strong>nalysis (EE-GAMA), a fragment-based quantum chemistry method that combines systematic many-body energy decomposition with electrostatic embedding based on overlapping spatial grid-based fragments. In EE-GAMA, electrostatic charge embedding is implemented within the Many- Overlapping Body (MOB) expansion framework, an approach rarely explored in previous studies. Each fragment is embedded in the electrostatic field generated by background point charges derived from Mulliken, Hirshfeld, or CM5 charge models, and both Geometry Dependent (GD) and Geometry Independent (GI) embedding schemes are investigated. Our primary goal is to accurately reproduce full-system energies at the MP2/6-311G(d,p) level. Benchmark calculations on neutral water clusters and hydronium clusters show that EE-GAMA achieves near full-system MP2 accuracy and significantly outperforms the non-embedded GAMA method. In charged systems, EE-GAMA effectively captures long-range electrostatics and consistently demonstrates that GD embedding offers greater accuracy than GI, underscoring the importance of environment-specific charge representation in highly polarized systems. While GI embedding offers computational simplicity, GD embedding provides enhanced reliability in such contexts. Overall, EE-GAMA offers an excellent balance between computational efficiency and accuracy and lays a strong foundation for the future development of advanced embedding schemes incorporating polarization and charge-transfer effects in large-scale quantum calculations.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1254 ","pages":"Article 115534"},"PeriodicalIF":3.0,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145263183","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Influence of a sequence of decoherence events on statistical measures of the time dependence of the flow of probability density relevant to constitutional isomerism by proton transfer","authors":"Karl Sohlberg","doi":"10.1016/j.comptc.2025.115525","DOIUrl":"10.1016/j.comptc.2025.115525","url":null,"abstract":"<div><div>The influence of a series of discrete decoherence events on metrics of the time-dependence of the flow of probability density is studied using three examples of constitutional isomerism by proton transfer. Both sampling frequency and fraction of the ensemble subjected to decoherence are explored. It is found that the frequency positions of the dominant peaks in the Fourier transform of time development of probability density are essentially unchanged by decoherence. Transfer times given by statistical confidences are shown to converge to the result obtained in the absence of decoherence with decreasing fraction of the ensemble subjected to decoherence. For sufficiently small time-steps, (high sampling frequency) the quantum Zeno effect is observed.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1254 ","pages":"Article 115525"},"PeriodicalIF":3.0,"publicationDate":"2025-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145263185","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Different pre-ignition reaction mechanisms for improving the combustion of fluoropolymers, containing different fluorine contents with aluminum particles","authors":"Bo Ni ,&nbsp;Jinyu Dai ,&nbsp;Hongwei Li ,&nbsp;Minglong Zhang ,&nbsp;Baozhong Zhu ,&nbsp;Jiuyu Chen ,&nbsp;Minggao Xu ,&nbsp;Yunlan Sun","doi":"10.1016/j.comptc.2025.115522","DOIUrl":"10.1016/j.comptc.2025.115522","url":null,"abstract":"<div><div>The use of fluoropolymers to modify aluminum (Al) powder has been demonstrated to improve the combustion efficiency. Different fluoropolymers have been observed to exert varying effects, but the reason remains unknown, so this work employs the ReaxFF-MD method combined with ignition experiments to examine the interaction process between PTFE, PVDF, THV and nano-sized Al particles (ns-Al). The pre-ignition reaction (PIR) mechanism of different fluoropolymers with ns-Al is distinct. For PTFE without H, its F atoms directly react with the oxide layer to form Al_xF_y or Al_xO_yF_z. This is referred to as PIR1. In H-containing PVDF and THV, the reaction between F atoms and H atoms with the oxide layer generates Al_xF_yH_z or Al_xO_yF_zH_n, which is classified as PIR2. The two PIR mechanisms exhibit notable differences. These results reveal the difference in the promotion of ns-Al ignition and combustion by fluoropolymers with different fluorine contents at the atomic level.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1254 ","pages":"Article 115522"},"PeriodicalIF":3.0,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145262612","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Cr adsorption and diffusion on LSCF surface: a first-principles study","authors":"Yuan-Zheng Lu ,&nbsp;Yu-Jing Liu ,&nbsp;Shu-Ming Zhang ,&nbsp;Kun Li ,&nbsp;Wen Yang","doi":"10.1016/j.comptc.2025.115514","DOIUrl":"10.1016/j.comptc.2025.115514","url":null,"abstract":"<div><div>To address the Cr poisoning issue in the cathode of Solid Oxide Fuel Cell, it is essential to investigate the adsorption and diffusion of Cr atoms on the surface of lanthanum strontium cobalt ferrite (LSCF) cathodes to uncover the Cr poisoning mechanism. This work systematically calculates the potential energy surface (PES) for the adsorption of Cr atoms on the La(Sr)<img>O-terminated (1 0 0) surface of LSCF. The possible diffusion paths of Cr atoms are derived from the PES, and the diffusion properties are further examined using the CI-NEB method. The results indicate that the lowest adsorption energy of the Cr atom is −6.760 eV at the Hollow sites. Two Cr diffusion paths across the entire surface in the x and y directions are also identified. The charge transfer among different atoms during the diffusion process is analyzed using Bader charge analysis, and the COHP method is employed to further reveal the bonding characteristic of Cr atoms on the surface. During the diffusion process, Cr atoms dynamically form and break bonds with surface oxygen atoms. This study provides theoretical insights to support subsequent experiments aimed at reducing the Cr poisoning effect on the LSCF surface.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1254 ","pages":"Article 115514"},"PeriodicalIF":3.0,"publicationDate":"2025-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145263176","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Deciphering solvent-driven intra- and intermolecular excited-state proton transfer mechanisms in 3BTHMB via TDDFT","authors":"Jiaan Gao,&nbsp;Xiaotong Guan,&nbsp;Siqi Wang,&nbsp;Yifu Zhang,&nbsp;Hui Li,&nbsp;Guangyong Jin","doi":"10.1016/j.comptc.2025.115529","DOIUrl":"10.1016/j.comptc.2025.115529","url":null,"abstract":"<div><div>The excited-state proton transfer (ESPT) process and photophysical properties of 3BTHMB molecule with different solvents are systematically studied via the density functional theory (DFT) and time-dependent DFT (TDDFT) methodologies. Our research confirms that the 3BTHMB molecule undergoes the excited state intramolecular proton transfer (ESItrPT) process in HEX and THF. In HEX, ESItrPT process is accompanied by the Twisted intramolecular charge transfer (TICT) process, and TICT is the cause of fluorescence attenuation. In THF, the observed short-wavelength emission originates from the Enol* state, whereas the ESItrPT-induced fluorescence from the Keto* state accounts for the long-wavelength emission. In DMF and MeOH, the molecule forms IEHB with the solvent. Under photoexcitation, we observe a strengthening of IEHBs in DMF, while in MeOH, this interaction is diminished. Importantly, despite the solvent-dependent modulations in IEHB strength, these interactions consistently facilitate the excited state intermolecular proton transfer (ESIerPT) process. This work provides a detailed understanding of the distinct photophysical behaviors of 3BTHMB in various solvents, offering valuable insights for experimental studies on efficient fluorescent probes for ESPT activity.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1254 ","pages":"Article 115529"},"PeriodicalIF":3.0,"publicationDate":"2025-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145262610","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"σ-Aromatic Envelope Geometry in Penta Coordinated Group 13-Bridged Transition Metal Carbonyl Clusters","authors":"Chhanda Paul,&nbsp;Sumit Satish Kadam,&nbsp;Shanti Gopal Patra","doi":"10.1016/j.comptc.2025.115531","DOIUrl":"10.1016/j.comptc.2025.115531","url":null,"abstract":"<div><div>In this study, five-membered ring containing penta-coordinated group 13 metal carbonyl clusters of the type [(<em>μ</em>-E){M(CO)₄}₅]²⁻, where E = B, Al, Ga, In, and M = Mn, Tc, Re are considered. DFT was employed for geometry optimization, revealing unusual but stable envelope-like structures, while aromatic character was evaluated using magnetic criteria, including Nucleus Independent Chemical Shifts (NICS), Gauge-Including Magnetically Induced Currents (GIMIC), etc. All the carbonyl clusters show <em>σ</em>-aromaticity. These studies reveal notable diatropic ring currents and highly negative NICS values in selected clusters of [(<em>μ</em>-E){M(CO)₄}₅]²⁻ species, indicative of strong σ-aromaticity. The σ-aromaticity is confirmed by NICS scan, NICS decomposition, and Natural Orbitals for Chemical Valence (NOCV). The trends in aromaticity are NICS: B &gt; Al &gt; Ga &gt; In (Mn), and B &gt; In ≥ Ga &gt; Al (Tc, Re); GIMIC: B &gt; Ga &gt; In &gt; Al (Mn), and B &gt; In ≥ Ga &gt; Al (Tc, Re).</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1254 ","pages":"Article 115531"},"PeriodicalIF":3.0,"publicationDate":"2025-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145262611","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Study on the esterification mechanism catalyzed by MIL-125 for the synthesis of 1,2-cyclohexanedicarboxylates","authors":"Zehua Si ,&nbsp;Zhongfeng Geng ,&nbsp;Baohe Wang ,&nbsp;Jing Ma ,&nbsp;Mingxuan Zhu","doi":"10.1016/j.comptc.2025.115532","DOIUrl":"10.1016/j.comptc.2025.115532","url":null,"abstract":"<div><div>Di(2-ethylhexyl)-1,2-cyclohexane dicarboxylate (DEHCH) is expected to function as a non-toxic plasticizer for replacing di(2-ethylhexyl) phthalate (DEHP). During the esterification for synthesis of DEHCH, the di-esterification process is usually known as rate control step. To better understand this process, Density Functional Theory (DFT) was utilized to investigate the mechanism of mono(2-ethylhexyl)-1,2-cyclohexane dicarboxylate with 2-ethylhexanol catalyzed by tetraisopropyl titanate [Ti(OiPr)₄], MIL-125, MIL-125-NH₂, and hydrated MIL-125. The results indicate that Ti(OiPr)₄ possesses a single coordinatively unsaturated Ti site and the reaction follows the bimolecular nucleophilic substitution (SN₂) mechanism, with an energy barrier as high as 184.97 kJ·mol⁻¹. Given Ti's high oxygen affinity and the abundance of reaction sites in metal-organic frameworks (MOFs), MIL-125, was innovatively selected for investigation. Simulated results show that the μ₂-O bridging between the two coordinatively unsaturated Ti atoms acts as an additional Brønsted base site, enhancing the reactivity. Meanwhile, the generated μ₂-OH assists in dehydration, serving as the rate-determining step with an energy barrier of 101.11 kJ·mol⁻¹. To further improve the dehydration, the -NH₂ group functionalized on the organic ligand and the dissociated -OH group from product water were strategically utilized as distinct Brønsted base sites. In MIL-125-NH₂, the energy barrier for dehydration was reduced to 33.31 kJ·mol⁻¹. Notably, in hydrated MIL-125, 2-ethylhexanol remains unadsorbed, lowering the energy barrier for dehydration to 25.24 kJ·mol⁻¹. These findings suggest that MIL-125 can transform the adverse impact of product water into a beneficial factor, thereby MIL-125 is recommended to catalyze the esterification of 1,2-cyclohexanedicarboxylic acid with 2-ethylhexanol.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1254 ","pages":"Article 115532"},"PeriodicalIF":3.0,"publicationDate":"2025-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145263175","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tuning the fused [1, 2, 4] triazolo-triazine core: enhancing detonation performance and safety through strategic functionalization","authors":"Kalpana Sharma ,&nbsp;Harshadip Bhagwan Deore ,&nbsp;Vikas D. Ghule ,&nbsp;Srinivas Dharavath","doi":"10.1016/j.comptc.2025.115530","DOIUrl":"10.1016/j.comptc.2025.115530","url":null,"abstract":"<div><div>To meet the need for energetic materials that combine both improved stability and high performance, this study presents the computational design and evaluation of four compounds based on the (Huang et al., 2020; Zhang et al., 2024; Muravyev et al., 2024 [1, 2, 4]) triazolo-triazine molecular backbone. The strategy aims to enhance the heat of formation, density, and detonation parameters of the compounds through the substitution of nitro, dinitromethyl, trinitromethyl, and nitramine functional groups. Notably, all the designed compounds exhibit high positive heats of formation (&gt; 438 kJ/mol) and deliver energetic performance (D &gt; 8.9 km/s, <em>P</em> &gt; 35 GPa) superior to that of RDX (D = 8.6 km/s, <em>P</em> = 34 GPa). Electrostatic potential, localized orbital locator-π, multicentre bond analysis, molecular planarity, and interaction region indicator analyses were conducted to understand the correlation between sensitivity and molecular structure. These energetic properties highlight the potential of the (Huang et al., 2020; Zhang et al., 2024; Muravyev et al., 2024 [1, 2, 4]) triazolo-triazine backbone with nitro functionalities in the development of safer and more efficient next-generation energetic materials.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1254 ","pages":"Article 115530"},"PeriodicalIF":3.0,"publicationDate":"2025-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145263184","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Size-dependent optical properties of tetrahedral copper nanoparticles: A CIS/DFT study","authors":"Gyun-Tack Bae","doi":"10.1016/j.comptc.2025.115526","DOIUrl":"10.1016/j.comptc.2025.115526","url":null,"abstract":"<div><div>The optical properties of tetrahedral copper nanoparticles (Cu₁₀-Cu₁₂₀) are studied using density functional theory and the configuration interaction singles method. The excitation energies were calculated for tetrahedral copper nanoparticles with different charge states. The resulting absorption spectra revealed size-dependent red-shifting of the maximum peaks, consistent with experimental and theoretical observations of localized surface plasmon resonance.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1254 ","pages":"Article 115526"},"PeriodicalIF":3.0,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145263177","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}